CN106068293A - The curable aqueous pu dispersions being manufactured by renewable resource - Google Patents

The curable aqueous pu dispersions being manufactured by renewable resource Download PDF

Info

Publication number
CN106068293A
CN106068293A CN201580011153.9A CN201580011153A CN106068293A CN 106068293 A CN106068293 A CN 106068293A CN 201580011153 A CN201580011153 A CN 201580011153A CN 106068293 A CN106068293 A CN 106068293A
Authority
CN
China
Prior art keywords
acid
polyalcohol
dispersions
aqueous
curable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201580011153.9A
Other languages
Chinese (zh)
Other versions
CN106068293B (en
Inventor
J.克朗
J.卢
I.瓦帕拉
Y.何
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of CN106068293A publication Critical patent/CN106068293A/en
Application granted granted Critical
Publication of CN106068293B publication Critical patent/CN106068293B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/428—Lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Curable aqueous pu dispersions, it is formed by following: make polyalcohol a) component react with excessive polyisocyanates b) to form polyurethane prepolymer, and described polyurethane prepolymer was neutralized and dispersed polyurethane using chain extender c) chain extension before forming final polyether polyols with reduced unsaturation water-borne dispersions.Polyalcohol a) component includes al) at least one non-ionic polyol, a2) there is at least one polyalcohol of at least one the ionic or potential ionic group including acid groups or its salt, and a3) at least one olefinic unsaturation monohydric alcohol or polyalcohol.Described polyol component comprises the carbon atom from renewable resource.Also disclose for prepare curable aqueous pu dispersions method, the purposes of described aqueous pu dispersions, the polyurethane of solidification.

Description

The curable aqueous pu dispersions being manufactured by renewable resource
The present invention relates to curable polyurethane aqueous (aqueous) dispersion being made up of renewable resource.More specifically, The present invention relates to the curable polyurethane aqueous dispersions being made up of the polyalcohol based on 1,4:3,6-bis-dewatering hexitol.
Dispersions of polyurethanes has many purposes in the industry.Such as dispersions of polyurethanes can be used for coating timber, plastics, gold Genus, glass, fiber, textile, leather, stone, concrete pottery or compound and other substrates, to provide to mechanical, chemical And/or the protection of ambient influnence.Dispersions of polyurethanes can also be used for adhesive, sealant, ink and other application, including make up Product are applied.
Dispersions of polyurethanes manufactures typically via being initially formed polyurethane prepolymer, and described prepolymer includes terminal groups Group, such as isocyanates (NCO) group, it can carry out chain extending reaction subsequently.Described polyurethane prepolymer or simply pre-polymerization Thing is typically formed to form isocyanate-terminated prepolymer with polyol reaction by excessive isocyanates.
Typically, polyalcohol provides flexible and elastic to polyurethane.Have attempted to use renewable resource, such as such as plant Oil, but such trial result in and lacks mechanical hardness required in numerous applications and the soft polyurethane of chemical-resistant.
Have attempted to use the dispersions of polyurethanes of isobide.Due to its structure, isobide result in polyurethane Fragility.
Chang et al. (" Linseed-oil-based waterborne UV/air dual-cured wood Coatings ", Progress in Organic Coatings 76 (2013), 1024-1031) disclose from a vegetable oil The curable dispersions of polyurethanes of UV that i.e. linseed oil is made.
Xia et al. (" Soybean Oil-Isosorbide-Based Waterborne Polyurethane-Urea Dispersions ", ChemSusChem 2011,4,386-391) disclose and be made up of soybean oil derivative and isobide Conventional polyurethanes dispersion.Isobide is used as monosomy chain extender rather than as the part of described polyalcohol.By Xia etc. Dispersions of polyurethanes disclosed in people is not that UV is curable.
WO 2011/047369 discloses use epoxidation or the triglyceride of PART EPOXY is for example epoxidised greatly The dispersions of polyurethanes that soya-bean oil is made.
United States Patent (USP) No.8,106,148 discloses the PEPA adding isobide for powdery paints.Polyester is many Unit's alcohol includes non-reproducible composition such as phthalic acid ester, to realize desired character.United States Patent (USP) No.8,106, 148 do not disclose the curable composition of UV.
WO 2011/098272 discloses the dispersions of polyurethanes based on reproducible diisocyanate, and it includes based on different The diisocyanate of sorbierite.WO 2011/098272 does not disclose the curable dispersions of polyurethanes of UV.
U.S. Patent Application Publication No.2005/0143549 discloses the polyurethane being formed by PEPA.Polyester Polymer is formed by dimer fatty acid and/or dimer fatty acid glycol, and can be additionally by Isosorbide-5-Nitrae: 3,6-bis-are dehydrated oneself Sugar alcohol such as isobide is formed.Polyurethane is used as hot melt adhesive.
Accordingly, there exist the demand to the following dispersions of polyurethanes based on renewable resource, it provides has required machine Tool intensity and chemical resistance, and be not soft or fragility.
The present invention relates to curable polyurethane aqueous dispersions and the method preparing such polyurethane aqueous dispersions.
One aspect of the present invention relates to the method preparing curable polyurethane aqueous dispersions, and the method includes:
I) make to include that following at least one polyol component a) reacts with b) at least one polyisocyanates: a1) non-from Sub-property polyalcohol, a2) there is at least one of at least one the ionic or potential ionic group including acid groups or its salt Polyalcohol and a3) the unsaturated monohydric alcohol of at least one olefinic and/or polyalcohol, the isocyanide of at least one of which polyisocyanates Hydroxyl (OH) group numbers relative to described at least one polyol component a) for acid esters (NCO) group numbers is excessive, its Described at least one polyol component a) include, especially at non-ionic polyol a1) in, from the carbon of renewable resource Atom, preferably described polyalcohol a1) derived from Isosorbide-5-Nitrae: 3,6-bis-dewatering hexitols
Ii) at least in part, preferably entirely neutralize described polyalcohol a2 with nertralizer) acid groups, and stir with Obtain polyurethane prepolymer water-borne dispersions；With
Iii) by reacting with isocyanate-reactive chain extenders, make step ii) described prepolymer chain extension.
The present invention also covers the water-borne dispersions of polyurethane prepolymer, and it can be in the described step of described method as defined above Rapid ii) at the end of obtain.
Another aspect of the present invention relates to curable polyurethane, and wherein said curable polyurethane is following by including A) at least one polyol component and b) at least one polyisocyanates react formation: a1) non-ionic polyol, a2) have Including at least one polyalcohol of at least one ionic or potential ionic group of acid groups or its salt and a3) at least one Plant the unsaturated monohydric alcohol of olefinic and/or polyalcohol, isocyanates (NCO) the group numbers phase of at least one of which polyisocyanates Hydroxyl (OH) group numbers at least one polyol component a) is excessive, wherein said at least one polyol component A) include, especially at non-ionic polyol a1) in, derive from the carbon atom of renewable resource, wherein polyalcohol a2) described Acid groups is in the form of acid or the form being at least partly neutralization, and the form being preferably at neutralization (neutralizes completely Form), and the chain extending reaction continuation that described reaction is by the chain extender with isocyanate-reactive in the second step.
The invention still further relates to curable waterborne compositions, it includes according to the present invention at least one water as defined above Property dispersions of polyurethanes is as curable adhesive.
The invention still further relates to the aqueous pu dispersions of the present invention at coating, paint, varnish, ink, or glue especially Purposes in stick, sealant and surface modifier, and described here aqueous pu dispersions is obtained (or making) The polyurethane of solidification.
Fig. 1 is that the polyalcohol using bio-based is to form the signal of the synthetic method of the curable dispersions of polyurethanes of UV Figure.
One aspect of present disclosure relates to curable polyurethane aqueous dispersions, and it is by least one polyalcohol Component reacts formation with at least one polyisocyanates, and at least one of which polyol component includes deriving from renewable resource, also It is defined as the carbon atom of the polyalcohol of biological multielement alcohol or biogenetic derivation.Such biological multielement alcohol preferably has14C weight Content makes14C/12C ratio is more than 0.1 × 10-12。
Phrase " deriving from the carbon atom of renewable resource " as used in this article refer to derived from, be derived from natural reproducible Resource such as such as living beings or the carbon atom based on plant or the resource being prepared by it.
According at least one embodiment, polyurethane prepolymer can be by least one polyol component a) and at least one Polyisocyanates b) reacts formation, and isocyanates (NCO) group numbers of at least one of which polyisocyanates is relative at least Hydroxyl (OH) group numbers of a kind of polyol component is excessive, and at least one of which polyol component a) includes deriving from The carbon atom of renewable resource (or being biological multielement alcohol as defined above).
" prepolymer " refers to alefinically unsaturated compounds as the term is used herein, and it includes one or more isocyanide Acid esters end group.Prepolymer can with comprise the functional group that for example can react in chain extending reaction with described prepolymer Other monomers of (i.e. isocyanate-reactive group), oligomer or compound reaction.
In at least one embodiment, polyol component a) includes a1) non-ionic polyol, a2) have at least one Individual at least one polyalcohol from sour ionic group and a3) the unsaturated monohydric alcohol of at least one olefinic or polyalcohol.
Thus, first theme of the present invention relates to curable polyurethane aqueous dispersions, wherein said curable gathering Urethane is formed by following:
I) make to include following a) at least one polyol component and b) at least one polyisocyanates react: a1) non-from Sub-property polyalcohol, a2) there is at least one the ionic or potential ionic group including acid groups or its salt at least one many Unit's alcohol and a3) the unsaturated monohydric alcohol of at least one olefinic and/or polyalcohol, the isocyanide of at least one of which polyisocyanates Hydroxyl (OH) group numbers relative at least one polyol component a) for acid esters (NCO) group numbers is excessive, Qi Zhongsuo State at least one polyol component a) to include, especially at non-ionic polyol a1) in, former from the carbon of renewable resource Son, preferably described polyalcohol a1) derived from Isosorbide-5-Nitrae: 3,6-bis-dewatering hexitols, and described polyalcohol a2) acid groups at It in sour form or the form being at least partly neutralization, is preferably at and continues after the form of neutralization, and described reaction Have
Ii) chain extending reaction (extension of the chain extender with isocyanate-reactive in the second step reaction)。
According at least one embodiment, non-ionic polyol a1) by making Isosorbide-5-Nitrae in polycondensation reaction: 3,6-bis-take off Water hexitol and the carboxylic acid reaction of other renewable glycol or diacid or higher functional, or by using Isosorbide-5-Nitrae: 3,6-bis-are dehydrated oneself Sugar alcohol is formed as the initiator of the ring-opening polymerisation of lactide.
1,4:3,6-bis-dewatering hexitol is selected from isobide, different mannide (isomannide) and different Chinese mugwort Du Alcohol, and described Isosorbide-5-Nitrae especially: 3,6-bis-dewatering hexitols are isobide.
According at least one embodiment, non-ionic polyol is by making Isosorbide-5-Nitrae in polycondensation polymerisation: 3,6-bis-take off Water hexitol and the carboxylic acid of at least one diacid or higher functional and optionally at least a kind of other glycol and/or polyalcohol are anti- Answer and formed.Phrase " glycol and/or polyalcohol ", as meant polyalcohol, the latter of glycol and/or higher functional in the present invention Mean the degree of functionality with at least 3.Described glycol is different from 1,4:3,6-bis-dewatering hexitol.As used in this article, short Language " carboxylic acid of higher functional " refers to the carboxylic acid with the acid functionality of at least 3.Preferably, described glycol and/or polynary Alcohol is renewable source, and therefore which is biological multielement alcohol.It is highly preferred that the carboxylic acid of described diacid or higher functional is also can Renewable source.
In at least one embodiment, non-ionic polyol can be by with Isosorbide-5-Nitrae: 3,6-bis-dewatering hexitols and extremely The polycondensation reaction of the carboxylic acid of few a kind of other glycol or polyalcohol and at least one diacid or higher functional is formed.Other The example of glycol includes (but not limited to) 1,2-ethylene glycol, 1,2-propane diols, 1,3-propane diols, 1,4-butanediol, 1,5-penta Glycol, 1,6-HD, 1,10-decanediol, 1,12-dodecanediol, 1,3 butylene glycol, 2,2-dimethyl-1,3-propane diols, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, DPG, tripropylene glycol, 1,4-and 1,6-dihydroxymethyl hexamethylene Alkane, C36-dimer diols (C36-dimer diol), hydroxyl pivaloyl group hydroxyl trimethylace tonitric ester and above ethoxy Base and/or propenoxylated derivative.Suitable three and the component of higher hydroxyl-functional include: glycerine, trimethylolpropane, Trimethylolethane, pentaerythrite, two glycerine, two-trimethylolpropane, two-pentaerythrite, D-sorbite and above ethoxy Base and/or propenoxylated derivative.
In at least one embodiment, non-ionic polyol a1) pass through Isosorbide-5-Nitrae: 3,6-bis-dewatering hexitols with at least The carboxylic acid reaction of a kind of diacid or higher functional is formed.According at least one embodiment, the carboxylic acid choosing of diacid or higher functional From: malonic acid, butanedioic acid, maleic acid, fumaric acid, itaconic acid, glutaric acid, citric acid, adipic acid, pimelic acid, decanedioic acid, 12 Docosandioic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), naphthalene dicarboxylic acids, C36-dimer fatty acid, C54-trimerization body fat Fat acid (three acid), PMA and above anhydride ester derivs.
According at least one embodiment, use Isosorbide-5-Nitrae: 3,6-bis-dewatering hexitols are as in the ring-opening polymerisation of lactide The initiator molecule of hydroxyl-functional forms non-ionic polyol a1).Lactide is the cyclic diester of lactic acid.Can open Other monomers of cyclopolymerization, such as lactone, may be additionally used for preparing the polyalcohol of co-polymerization.So, according to a concrete reality Execute scheme, at least one non-ionic polyol a1) include or for by making Isosorbide-5-Nitrae: 3,6-bis-dewatering hexitols and hydroxyl-functional Ground monocarboxylic acid reaction or by make 1,4:3,6-bis-dewatering hexitol, especially in ring-opening polymerisation as initiator molecule with interior Ester, preferably react formed polyalcohol with caprolactone.Suitable lactone includes α, α dimethyl beta-propiolactone, λ-Ding Nei Ester and 6-caprolactone, and 6-caprolactone is preferred lactone.
According at least one embodiment, Isosorbide-5-Nitrae: amount in polyol component for 3,6-bis-dewatering hexitols can be used to control The glass transition temperature (Tg) of the polyurethane preparing and hardness.For example, described polyalcohol a), especially polyalcohol a1) can Comprise 1,4:3,6-bis-dewatering hexitol of about 10 weight % to about 75 weight %.The character of polyurethane also can be by using one Or multiple other polyalcohols not comprising 1,4:3,6-bis-dewatering hexitol are with to include 1,4:3,6-bis-dewatering hexitol many The combination of unit's alcohol controls.
According at least one embodiment, other renewable resource compound can be used for substituting Isosorbide-5-Nitrae: 3,6-bis-are dehydrated oneself Sugar alcohol or used in addition to 1,4:3,6-bis-dewatering hexitol.For example, non-ionic polyol a1) can for PEPA simultaneously Including the renewable type of (or can derived from) polyacid and polyalcohol, such as unrighted acid, C36And C54Dimer and three Interpolymer product and furan derivatives, such as 2,5-furan dicarboxylic acid.These and other derives from the exemplary polynary of renewable resource Alcohol and polyacid or cyclic ester are shown in hereafter.
Described at least one polyol component a) also includes a2) there is at least one including acid groups or its salt especially At least one polyalcohol of ionic or potential ionic group.Described acid groups is selected from carboxyl (-CO2H), sulfonic group (- SO3H), sulfonyl (-SO2H), phosphoryl (-PO3H2) and phosphono (-PO2H).According at least one embodiment, at least one Polyalcohol a2) acid groups selected from carboxyl, sulfonic group or sulfonyl, and preferably carboxyl.Comprise the polyalcohol of acid groups A2) example includes, but are not limited to this, and 2-carboxyl-1,3-PD, 2-sulfo group-1,3-PD, 2-methyl-2-carboxyl are own Glycol, 3-methyl-3-carboxyl hexylene glycol.4-methyl-4-carboxyl hexylene glycol.2-ethyl-2-carboxyl-1,3-propane diols.2-ethyl- 2-carboxyl butanediol, dihydromethyl propionic acid, dimethylolpropionic acid, 2-sulfo group-1,4-butanediol, 2,5-dimethyl-3-sulfo group-2, 5-hexylene glycol, Tau, N-(1,1-dimethyl-2-ethoxy)-3-amino-2-hydroxy-propanesulfonic acid, 2-amino second ammonia Base ethyl sulfonic acid and above salt.
At least one polyol component farther includes a3) the unsaturated a3.1 of at least one olefinic) monohydric alcohol and/or A3.2) polyalcohol.Preferably, described monohydric alcohol a3.1) or polyalcohol a3.2) can have per molecule 1-5, preferably 2-5 Ethylenically unsaturated group, more preferably (methyl) acrylate group.Preferably, described polyalcohol a3.2) OH degree of functionality can From 2 to 5 changes, and preferably described olefinic unsaturated polyol a3.2) it is olefinic unsaturated diol.
According to a3.1) really to introduce terminal ethylenic unsaturated for the monohydric alcohol that defines, and glycol introduces laterally unsaturated, and more The polyalcohol of Gao Guanneng creates following apparatus derivatorius, and it is in polyurethane backbone skeleton (horizontal or laterally unsaturated) and dividing in grafting Branch (laterally unsaturated, but on the polyurethane branch of grafting) has degree of unsaturation on both.According to a concrete embodiment party Case, described polyol component a3) be monohydric alcohol a3.1) and polyalcohol a3.2) mixture.According at least one embodiment, The unsaturated monohydric alcohol of at least one olefinic or polyalcohol include monohydric alcohol or glycol.The unsaturated monohydric alcohol a3.1 of olefinic) or polynary Alcohol a3.2) example include, but not limited to polyester (methyl) acrylate, epoxy (methyl) acrylate, polyethers (methyl) third Olefin(e) acid ester, polyurethane (methyl) acrylate comprise (methyl) acrylate of hydroxyl with other.As (the first comprising hydroxyl Base) example of acrylate, can enumerate but be not limited to, monohydric alcohol: hydroxy alkyl (methyl) acrylate, wherein alkyl is at C2Extremely C4In can be alkoxylated；Or there is multifunctional (methyl) acrylate of free hydroxyl group, as can be alkoxylated three Hydroxymethyl-propane two (methyl) acrylate, double trimethylolpropane three (methyl) acrylate that can be alkoxylated, can quilt Pentaerythrite five (methyl) acrylate of alkoxylate.Be used for a3.2 as suitable) the polyalcohol (methyl) comprising hydroxyl The example of acrylate, can enumerate: trihydroxy methyl list (methyl) acrylate (glycol), double trihydroxy methyl two (methyl) acrylic acid Ester (glycol), double trihydroxy methyl (methyl) acrylate (triol), pentaerythrite two (methyl) acrylate (glycol), Ji Wusi Alcohol list (methyl) acrylate (triol), dipentaerythritol four (methyl) acrylate (glycol), dipentaerythritol two (methyl) Acrylate (tetrol), dipentaerythritol three (methyl) acrylate (triol), all above by alkoxylate potentially.Alcoxyl The unit of base can be ethyoxyl and/or propoxyl group and/or four methylene epoxides (tetramethylenoxy), at least one of which Oxyalkyl units substitutes OH (by OH), and preferably 1-10 and more preferably 1-6 oxyalkyl units substitute OH.
In at least one embodiment, at least one polyalcohol a) component includes the carbon atom deriving from renewable resource. For example, the carbon atom of renewable source can be by non-ionic polyol a1), comprise the polyalcohol a2 of acid groups) and/or olefinic is not Saturated monohydroxy alcohol or polyalcohol a3) provide.In at least one embodiment, the carbon atom of renewable source can be by nonionic Polyalcohol a1) and/or the unsaturated monohydric alcohol of olefinic or polyalcohol a3) provide.According at least one preferred embodiment, non-from Sub-property polyalcohol a1) include the source carbon atom that can originate again.
The use of the natural carbon-based starting material with renewable source can be by the carbon of the composition participating in end product The isotope ratio of atom detects.This is because, the material producing unlike fossil material, reproducible parent material is constituted Material comprises14C.It is actually 3 kinds of isotopic mixtures from all carbon samples that organism (animal or plant) is drawn:12C (accounting for～98.892%),13C (～1.108%) and14C (～1.2 × 10-10%).Bio-tissue14C/12C ratio is at air In be identical.In the environment,14C exists with two kinds of principal modes: inorganic form such as carbon dioxide (CO2), and organic Form for example adds the carbon in organic molecule.In organism,14C/12C ratio keeps metabolism constant, because carbon continues with environment Ground exchange.Due to14The ratio of C is substantially constant in an atmosphere, thus it is identical in organism, as long as it is alive , because it absorbs14C absorbs such as it12C.Averagely14C/12C ratio is equal to 1.2 × 10-12。12C is stable, say, that In given sample,12The quantity of C atom is constant in time.Right14For C, it is radioactive, and biology is each Gram carbon, comprises enough14C isotope is to give the transformation (disintegration) of per minute 13.6.Relate to14The transformation of C is normal Half-life (or time period) T of number1/2It is 5730.Due to this time, thus14C content is initiateing from this natural reproducible The practice being extracted into end product manufacture of material is considered to be constant.
In at least one embodiment, at least one polyol component a) of present disclosure has14C weight content makes ?14C/12C ratio is more than 0.1 × 10-12.According at least one embodiment, at least one polyol component a) has14C weight Content makes14C/12C ratio more than and preferably more than 0.2 × 10-12, be more than 0.4 × 10-12, be more than 0.6 × 10-12, be more than 0.8×10-12Or it is more than 1.0 × 10-12。
It is currently, there are at least two for measuring sample14The different technologies of C content:
By liquid scintillation spectrometry (liquid scintillation spectrometry)；Or
By mass spectrography, wherein sample is reduced into oil ink or gaseous state CO2And it is analyzed in a mass spectrometer.Should Technology use accelerator and mass spectrograph with from12C ion isolation goes out14C ion simultaneously thus measures two kinds of isotopic ratios.
For measurement of species14All these methods of C content at standard ASTM D 6866 (D6866-06 especially) and Standard ASTM D 7026 (7026-04 especially) is explicitly described.The measuring method being preferably used is at standard ASTM D Mass spectrography (accelerator mass spectrometry) described in 6866-06.
As alkoxide component a3 as defined above) the example of epoxy (methyl) acrylate include acrylic acid or methyl-prop Olefin(e) acid or the product of its mixture and glycidol ether or ester.This glycidol ether or ester can have aliphatic series, cyclic aliphatic Or aromatic structure, and comprise 2 up to about 6 epoxy-functionals.The material of diepoxy official energy is preferred.Glycidol Ether can be prepared from the epoxide of the precursor of hydroxyl-functional and such as chloropropylene oxide.The many hydroxyl-functionals being listed above Component is applicable to prepare aliphatic series glycidol ether.Instantiation for aliphatic series glycidol ether precursor includes: 1,4-butanediol, 2,2-dimethyl-1,3-propane diols, 1,6-HD, 1,4-and 1,6-hydroxymethyl-cyclohexane, PEG, poly-(the third two Alcohol), poly-(tetramethylene glycol), trimethylolpropane, pentaerythrite, glycerine and D-sorbite.For aromatic glycidyl ethers The instantiation of precursor includes: bisphenol-A, Bisphenol F and resorcinol.
Suitable epoxy (methyl) acrylate may also comprise acrylic or methacrylic acid or its mixture and natural oil And component fatty acids, such as soybean, linseed, castor oil, rapeseed, safflower, olive, pine tar and other people in the art Member is by the product of the known epoxy derivative of those.
The example of suitable polyethers (methyl) acrylate includes acrylic or methacrylic acid or its mixture and polyethers The ester of polyalcohol.Suitable PPG can be the linear or branched material comprising ehter bond and terminal hydroxyl.Polyether polyols Alcohol can be prepared by the ring-opening polymerisation of cyclic ether such as oxolane or epoxyalkane and initiator molecule.Suitable initiator Molecule includes water, alcohol (including polyalcohol) and amine.The example of suitable amine includes: ethylenediamine, 4,4 '-diamino-diphenyl Methane, diethylenetriamine and hydroxylamine such as monoethanolamine and diethanol amine.The example of suitable epoxyalkane includes: epoxy second Alkane, expoxy propane, epoxy butane, chloropropylene oxide and glycidol.Polyethers (methyl) acrylate can individually or with combination Form uses.
The example of polyurethane (methyl) acrylate include described below two-or polyisocyanates react with isocyanates Property the addition polymerization product of the unsaturated component of olefinic, the unsaturated component of the olefinic of described isocyanate-reactive hereinbefore by Be described as polyester-, epoxy-or polyethers (methyl) acrylate, or hereinafter will be described as comprising monosomy hydroxyl (methyl) acrylate.
Comprise the example of (methyl) acrylate of monosomy hydroxyl for having simple glycol, triol, tetrol or polyalcohol Acrylate, methacrylate or mixed ester, wherein carry out esterification process so that residual hydroxy groups is retained in end product In.Example includes following (methyl) acrylate: 1,2-ethylene glycol, 1,2-propane diols, 1,3-propane diols, 1,4-butanediol, 1,5-pentanediol, 1,6-HD, 1,10-decanediol, 1,12-dodecanediol, 1,3 butylene glycol, 2,2-dimethyl-1,3- Propane diols, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, DPG, tripropylene glycol, 1,4-and 1,6-dihydroxy first Butylcyclohexane, glycerine, trimethylolpropane, trimethylolethane, pentaerythrite, two glycerine, two-trimethylolpropane, two-season Penta tetrol and D-sorbite.(methyl) acrylate comprising monosomy hydroxyl can individually or use as a mixture.
According at least one embodiment, polyisocyanates b) includes at least two isocyanate functional group.At least one In individual embodiment, polyisocyanates b) can include the diisocyanate with two isocyanate functional groups, such as aliphatic series two Isocyanates (such as IPDI).In other embodiments, polyisocyanates can include multiple isocyanic acid Ester group, such as three or four or more isocyanate groups.
The non-limiting examples of compound can include polyisocyanates, and described polyisocyanates includes two or polyisocyanates Such as per molecule has the aliphatic series of at least two isocyanate functional group, aromatics and cyclo-aliphatic structure.Suitable polyisocyanates B) example of component includes: IPDI, hexamethylene diisocyanate, 2,3,3-tri-methyl hexamethylene two Isocyanates, 4,4 '-dicyclohexyl methyl hydride diisocyanate, 1,5-naphthalene diisocyanate, 2,4-or 2,6-toluene diisocynate Dimer or the tripolymer of ester and their isomer mixture, 4,4 '-methyl diphenylene diisocyanate and each of which spread out Biology and mixture thereof.Described polyisocyanates also can be modified by allophanate groups.
By creating chlorinated isocyanurates (particularly in diisocyanate trimer) or biuret structure (particularly two In uretdione) the polyisocyanates also suitable mixture as isocyanates that formed.There is the polyisocyanate of 3 degrees of functionality Cyanate b) can be the chlorinated isocyanurates triisocyanate with tris isocyanurate ring, and it can provide high heat endurance Energy.Based on the renewable resource of polyisocyanates be for example described in for example in WO 2011/098272 page 2 the 12nd walk to the 6th Page the 10th row, it is incorporated into this as reference, it is possible to use according to present disclosure.
According at least one embodiment, prepolymer can be by above-described polyol component a) and polyisocyanates b) Reaction is formed.In at least one embodiment, isocyanates (NCO) group numbers of at least one polyisocyanates b) is relative It is excessive in hydroxyl (OH) group numbers of at least one polyol component a).
In at least one embodiment, polyalcohol a2) acid groups can before the dispersing or period by add alkali and in With the form becoming salt.Suitable alkali includes inorganic hydroxide or carbonate and amine and combination.At at least one preferably In embodiment, polyalcohol a2) acid groups neutralize with tertiary amine.
The polyalcohol of the present invention may be alternatively used for formed dispersions of polyurethanes, according to that submit on November 22nd, 2013, Entitled " Solvent-free aqueous polyurethane dispersions and methods of producing U.S. Provisional Patent Application No.61/907 of solvent-free aqueous polyurethane dispersions ", 434, and simultaneously submit to, entitled " Solvent-free aqueous polyurethane dispersions and The United States Patent (USP) of methods of producing solvent-free aqueous polyurethane dispersions " Provisional application No.61/986, method disclosed in 165, it is integrally incorporated in this them as reference.
Dispersions of polyurethanes is used as other component and is formed.
According at least one embodiment, at least one polyalcohol a) and at least one polyisocyanates b) can be curable Or reaction in the presence of reactive diluent, this diluent mean can during this solidification with described olefinic unsaturated poly-ammonia The unsaturated diluent of the olefinic of ester coreaction.Curable or reactive diluent is at least one ethylenically unsaturated monomer or low Polymers, preferably monomer, it can compatible with described curable polyurethane (non-solve mixed (non demixing)).Curable is dilute Release the material that agent for example can include having two or more ethylenically unsaturated groups, as example, (methyl) acrylate group. Can be that monosomy or oligomeric curable diluent can individually or use in combination.Especially, these are anti- Answering property diluent should not have isocyanate-reactive group, such as hydroxyl or amido.The example of suitable monomer class include with Under (methyl) acrylate: 1,2-ethylene glycol, 1,2-propane diols, 1,3-propane diols, 1,4-butanediol, 1,3 butylene glycol, 1, 5-pentanediol, 1,6-HD, 1,10-decanediol, 1,12-dodecanediol, 1,3 butylene glycol, 2,2-dimethyl-1,3-third Glycol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, TEG, DPG, tripropylene glycol, 1,4-and 1, 6-hydroxymethyl-cyclohexane, glycerine, trimethylolpropane, trimethylolethane, pentaerythrite, two glycerine, two-trihydroxy methyl third Alkane, two-pentaerythrite, D-sorbite and above alkoxy derivative.Many such materials can be from Sartomer conduct " SR " product obtains.Reactive diluent helps the minimum film of reduction system to form temperature (MFFT), promotes particle coalescence, and And additionally aid the coating property of solidification.Then, according to particular options, the polyether polyols with reduced unsaturation water-borne dispersions of the present invention enters one Step includes that curable ethylenically unsaturated monomer serves as curable diluent, and this diluent be present in as defined above and In the reaction forming relevant step i) of prepolymer.In fact, described diluent is used as the reaction diluent in step i), and And during the solidification of curable polyether polyols with reduced unsaturation, it is used as reactive diluent.
The curable diluent of low cluster include polyester as above-, polyethers-or urethane (methyl) acrylate, remove When as reactive diluent, hydroxyl (methyl) acroleic acid esterification by fully.Many such products can be from Sartomer obtains as " CN " product.
Partly neutralize, preferably entirely neutralize polyalcohol a2) acid groups after, the poly-ammonia obtaining in dispersions Ester prepolymer needs to stand the chain extending reaction with chain extender c), thus divides at the final water-based polyurethane polymer according to the present invention A prose style free from parallelism forms described polyether polyols with reduced unsaturation.Chain extension improves the molecular weight of polyurethane prepolymer further, and/or is altered or modified The character of final described curable polyurethane.For example, may select chain extender c) to change/to regulate hardness, weatherability, flexibility Or adhesivity.Chain extender c) is selected from polyalcohol and polyamines, such as such as glycol and diamines.It is preferably carried out scheme at least one In, chain extender c) is selected from polyamines and is more preferably selected from diamines.
Chain extender can include the functional group that two or more isocyanates end groups with polyurethane prepolymer react. In at least one embodiment, chain extender includes Liang Ge isocyanate-reactive functional group and acts on to extend polyurethane.? In other embodiments, chain extender can include three or more functional groups, and acts on extending polyurethane chain, and increases chain Branch but do not carry out any crosslinking.In at least one embodiment, can use and comprise Liang Ge functional group and three or more The mixture of the chain extender of individual functional group.In the case that the equal Guan Nengdu (throughout component a+b+ chain extender) of overall number is higher than 2, then Occur branched.The curable polyurethane of the present invention can have linear or branched chain structure, but does not has any cross-linked structure to deposit It is in described curable polyether polyols with reduced unsaturation, before its aqueous dispersion and chain extension or afterwards.At population mean In the case that degree of functionality is higher than 2, skilled person will know how to prevent any cross-linking reaction.Generally, little by little by one Reactant adds in another kind of, and so control reactant ratio (ratio to NCO reactive group for the NCO group) and The conversion of these groups, to meet as disclosed in Macromolecules, vol.9, the 199-221 page (1976) Macosko-Miller relation.This relation is about the equivalent r at A and BcWith restriction conversion ratio (limit conversion) xg (being limited by crosslinked gelation) is to reactant A and B respective average number degree of functionality fAAnd fBCritical ratio, wherein A is Corresponding to polyalcohol a), B corresponds to the reactant of polyisocyanates b), reacts because it considers that prepolymer is formed, and In the case of polyurethane chain extending reaction, A may correspond to chain extender c), and B corresponds to NCO prepolymer, wherein to be met Macosko-Miller contextual definition is as follows:
rc*xg 2=1/ [(fB-1)*(fA-1)
In at least one embodiment, it is used for forming dispersions of polyurethanes or the reactant mixture of prepolymer may also include Catalyst and/or other additives, as example, inhibitor, filler, stabilizer, light inhibitor, pigment etc..Outer surface activity Agent is unnecessary and only optionally can be used.
According at least one embodiment of present disclosure, polyether polyols with reduced unsaturation water-borne dispersions is radiation-curable Or the aqueous pu dispersions of peroxide-curable.In at least one embodiment, dispersions of polyurethanes can be by cruelly It is exposed to actinic radiation to solidify.According at least one embodiment, dispersions of polyurethanes is to be solidified by being exposed to ultraviolet light 's.
The second theme of the present invention relates to preparing above according to curable polyurethane aqueous as described in present invention definition The method of dispersion, the method comprises the following steps:
I) make to include that following at least one polyol component a) reacts with b) at least one polyisocyanates: a1) non-from Sub-property polyalcohol, a2) there is at least one of at least one the ionic or potential ionic group including acid groups or its salt Polyalcohol and a3) the unsaturated monohydric alcohol of at least one olefinic and/or polyalcohol, the isocyanide of at least one of which polyisocyanates Hydroxyl (OH) group numbers relative to described at least one polyol component a) for acid esters (NCO) group numbers is excessive, its Described at least one polyol component a) include, especially at non-ionic polyol a1) in, from the carbon of renewable resource Atom, preferably described polyalcohol a1) derived from Isosorbide-5-Nitrae: 3,6-bis-dewatering hexitols
Ii) at least in part, preferably entirely neutralize described polyalcohol a2 with nertralizer) acid groups, and stir (point Dissipate) to obtain polyurethane prepolymer water-borne dispersions；With
Iii) by with isocyanate-reactive chain extenders c) reaction, make step ii) described prepolymer chain extension.
Another theme being covered by the present invention by define immediately above, include the step i) defining immediately above and Ii) the polyurethane prepolymer water-borne dispersions that method obtains, and described polymer is in described step ii) at the end of, expanding Step iii of chain) obtain before.
The present invention also covers curable waterborne compositions really, it include according to the present invention as herein defined or At least one aqueous pu dispersions being obtained by manufacture method defined herein according to the present invention is as curable Adhesive.More particularly, described curable composition is selected from curable coating, paint, varnish, ink combination especially Thing, or selected from adhesive, sealant or cosmetic composition.
Another theme of the present invention relates to water-based polyurethane polymer dispersion of the present invention in coating, especially at oil Paint, varnish and ink, or in adhesive, the purposes at sealant and in cosmetics.
Finally, the present invention covers the finished product of cured polyurethane, and it derives from aqueous poly-ammonia according to defined in the present invention The solidification of ester dispersion, the polyurethane of more particularly described solidification is used as coating, preferably paint, varnish and ink, or is used as Adhesive, be used as sealant or be used as cosmetics.
According at least one embodiment, the polyether polyols with reduced unsaturation water-borne dispersions of present disclosure can be used for coating, special Other ground coated article, as example, timber, metal, plastics, pottery, composite article, glass, fiber, textile, leather, stone Head, concrete and other materials.After film formation, can use the dispersions of polyurethanes coated article being subsequently cured.
The polyether polyols with reduced unsaturation water-borne dispersions of present disclosure can be used for forming coating, especially paint, varnish, oil Ink, it provides protection from machinery, chemistry and/or ambient influnence.In other embodiments, dispersions of polyurethanes can be used as glue Stick, sealant, surface modifier, surface coating and cosmetics.
In at least one embodiment, the polyether polyols with reduced unsaturation water-borne dispersions of present disclosure can be used as curable Adhesive is to form radiation-curable or peroxide-curable waterborne compositions.
The dispersions of polyurethanes of present disclosure can also be used for adhesive, sealant, ink and other application, for example, provide Superficial makings or sense of touch effect.
The polyurethane coating being formed by the dispersions of polyurethanes of present disclosure can be used for providing scratch resistance, resistance to abrasion And mar proof；UV protects；Corrosion resistance；Appearance, for example smooth or smooth appearance；Chemistry and spot patience；Water-fast Xie Xing；Anti-flammability；Antimicrobial acivity；Conduction or insulation；Barrier or permeability to gas；Adhesive force；Haptic effect, for example Soft feel；Property easy to clean and anti-fingerprint.The character of produced polyurethane coating can be present in the above by changing They body in the amount of component control.
Embodiment
Embodiment 1
Following scheme is used to prepare PEPA: 1,3-propane diols (177g), isobide (681g), butanedioic acid (551g), be all from renewable resource, 70% methanesulfonic acid (17g) together with toluene (388g) and in water load to be furnished with for Collect the reaction vessel of the side arm of the water disengaging.Heating the mixture to 112 DEG C to reach 21 hours, the now generation of water stops substantially Only.After removing toluene by vacuum distillation, final polyester product is the viscosity liquid of the hydroxyl value with 200mg KOH/g Body.
Embodiment 2
Reach a few hours by being heated to 120 DEG C in the presence of stannous octoate catalyst, by isobide (98g) and d, l- Lactide (240g) prepares PEPA.Final polyester product is the viscous liquid of the hydroxyl value with 211mg KOH/g.
The preparation of the curable dispersions of polyurethanes of embodiment 3-UV (UV-PUD)
Be filled be applicable to the standby reaction vessel of polyurethane two-trimethylolpropane trimethacrylate (OH value= 163mg KOH/g, 206g), the PEPA (388g) of embodiment 1, dihydromethyl propionic acid (113g), MeHQ (4.8g), two The trimethylolpropane trimethacrylate (Sartomer SR454,1603g) of dibutyl tin laurate (3.2g) and ethoxylation, And mixture is heated to 50 DEG C.IPDI (888g) added between 30 minutes, put forward temperature simultaneously Up to 70 DEG C.It is constant that reaction is maintained at 70 DEG C of NCO% until titration, is down to 55 DEG C at a temperature of now inciting somebody to action.With acutely Triethylamine (85g), deionized water (4577g) are added in stirring subsequently.After 5 minutes, add the second being dissolved in deionized water (93g) Diamines (92g) and continue to be stirred for up to other 2 hour.After by 100 Mm filter bag filtrations, final dispersion tool Have following character: w/w% solid=42.0,25 DEG C when viscosity=6.1mPa.s (6.1cP), average grain diameter=114nm and pH =7.23.
The preparation of the curable dispersions of polyurethanes of embodiment 4-UV (UV-PUD)
Be filled be applicable to the standby reaction vessel of polyurethane two-trimethylolpropane trimethacrylate (OH value= 163mgKOH/g, 130g), the PEPA (101g) of embodiment 1, poly-(1,3-PD) (200g) (product of DuPont, 1000MW), three hydroxyl first of dihydromethyl propionic acid (78g), MeHQ (3.3g), dibutyl tin laurate (2.2g) and ethoxylation Base propane triacrylate (Sartomer SR454,1110g), and mixture is heated to 50 DEG C.Isophorone two isocyanide Acid esters (590g) added between 30 minutes, improved temperature to 70 DEG C simultaneously.Reaction is maintained at 70 DEG C until titration NCO% is constant, is down to 55 DEG C at a temperature of now inciting somebody to action.With being stirred vigorously, add triethylamine (59g), deionized water subsequently (3135g).After 5 minutes, add the ethylenediamine (58g) that is dissolved in deionized water (64g) and to continue to be stirred for up to other 2 little When.After by 100 Mm filter bag filtrations, final dispersion has following character: w/w% solid=41.3,25 DEG C When viscosity=10.2mPa.s (10.2cP), average grain diameter=126nm and pH=7.2.
The preparation of the curable dispersions of polyurethanes of embodiment 5-UV (UV-PUD)
Defer to the program of embodiment 4, but use following formula: two-trimethylolpropane trimethacrylate (OH value= 163mg KOH/g, 124g), the PEPA (210g) of embodiment 1, poly-(1,3-PD) (140g) (product of DuPont Product, 1000MW), dihydromethyl propionic acid (84g), MeHQ (3.6g), the three of dibutyl tin laurate (2.4g) and ethoxylation Hydroxymethyl-propane triacrylate (Sartomer SR454,1195g), IPDI (631g), triethylamine (63g), deionized water (3408g) and ethylenediamine+water (68g, 70g).After by 100 Mm filter bag filtrations, final Dispersion has following character: w/w% solid=41.1,25 DEG C when viscosity=10.2mPa.s (10.2cP), average grain diameter= 176nm and pH=7.25.
The preparation of the curable dispersions of polyurethanes of embodiment 6-UV (UV-PUD)
It is filled with dihydromethyl propionic acid (85g), MeHQ (2.8g), two bays be applicable to the standby reaction vessel of polyurethane Acid dibutyl tin (1.9g), the trimethylolpropane trimethacrylate (Sartomer SR454,1204g) of ethoxylation and different Buddhist Your ketone diisocyanate (572g), and mixture is heated to 70 DEG C until the NCO% content of titration fall to approximately 7.9%. Then two-trimethylolpropane trimethacrylate (OH value=163mg KOH/g, 98g), the PEPA of embodiment 2 are added (145g), poly-(1,3-PD) (298g) (product of DuPont, 1000MW), MeHQ (3.6g) and other 1.9g bis-bay Acid dibutyl tin, and keep the temperature at 70 DEG C until realizing constant NCO% content.Temperature is reduced to 55 DEG C and companion Add triethylamine (64g), deionized water (3359g) with being stirred vigorously subsequently.After 5 minutes, add and be dissolved in deionized water (120g) ethylenediamine (49g) in and continue to be stirred for up to other 2 hour.After by 100 Mm filter bag filtrations, Whole dispersion has following character: w/w% solid=40.6,25 DEG C when viscosity=12.6mPa.s (12.6cP), average particle Footpath=118nm and pH=7.79.
The preparation of the curable dispersions of polyurethanes of embodiment 7-UV (UV-PUD)
It is filled with dihydromethyl propionic acid (115g), MeHQ (4.9g), February be applicable to the standby reaction vessel of polyurethane Dilaurylate (3.3g), the trimethylolpropane trimethacrylate (Sartomer SR454,1633g) of ethoxylation and different Isophorone diisocyanate (888g), and mixture be heated to 70 DEG C until titration NCO% content fall to approximately 8.9%.Then two-trimethylolpropane (179g), the embodiment of the acroleic acid esterification with OH value=163mg KOH/g are added The PEPA (220g) of 2, poly-(1,3-PD) (223g) (product of DuPont, 1000MW), and temperature is kept At 70 DEG C until realizing constant NCO% content.Temperature is reduced to 55 DEG C, and adds triethylamine subsequently with being stirred vigorously (87g), deionized water (4595g).After 5 minutes, add the ethylenediamine (94g) being dissolved in deionized water (164g) and continue It is stirred for up to other 2 hour.After by 100 Mm filter bag filtrations, described final dispersion has following character: w/ W% solid=41.1,25 DEG C when viscosity=8.9mPa.s (8.9cP), average grain diameter=173nm and pH=7.17.
The solidification of embodiment 8-embodiment UV-PUD and test
In order to carry out the test of solidification and coating property, add UV-PUD to simple formulation, based on solid Described formulation is added 1% association thickener (associative by 63.5%UV-PUD (after regulation to 35% solid) Thickener), 0.5% leveling agent (leveling agent) and 5%500 light trigger compositions.With The wet-film thickness drop-down (drawdown) of 152.4 μ (6 mil), on Leneta piece, glass plate or aluminium sheet, is depended on to be run Test.In order to ensure fully removing water from described film and not affecting test, result be dried carry out reaching 30 minutes at 25 DEG C and 60 DEG C reach 30 minutes (similar to hereafter those displays in 25 DEG C of dryings 10 minutes and the test carrying out after 10 minutes at 60 DEG C Result).Solidified by the Inpro UV with two mercury bulbs by running with 15.24m/ minute (50fpm: feet per minute) Unit, the film being dried is with 410mJ/cm2UVA energy is cured.
Result from the test of cured film is shown in Table 1.
The coating property of table 1:UV-PUD solidification
*1=is best, and 5=is worst.Dyeing test is to use mustard, catsup, coffee, olive oil and ethanol to follow KCMA Program is carried out.Taber abrasion by with CS17 wheel under 1kg load the weight loss of every 200 circulations carry out 1000 and follow Ring is measured.

Claims (20)

1. curable polyether polyols with reduced unsaturation water-borne dispersions, wherein said curable polyurethane is formed by following:
I) a) include that following at least one polyol component reacts with b) at least one polyisocyanates: a1) nonionic is many Unit alcohol, a2) have at least one the ionic or potential ionic group including acid groups or its salt at least one polyalcohol, And a3) the unsaturated monohydric alcohol of at least one olefinic and/or polyalcohol, the isocyanates of at least one of which polyisocyanates (NCO) hydroxyl (OH) group numbers relative at least one polyol component a) for the group numbers is excessive, wherein said extremely Few a kind of polyol component a) includes, especially at non-ionic polyol a1) in, from the carbon atom of renewable resource, excellent Polyalcohol a1 described in selection of land) derived from Isosorbide-5-Nitrae: 3,6-bis-dewatering hexitols, and described polyalcohol a2) acid groups be in acid Form or the form being at least partly neutralization, be preferably at after the form of neutralization, and described reaction and continue to have:
Ii) chain extending reaction of the chain extender with isocyanate-reactive in the second step.
2. aqueous pu dispersions according to claim 1, at least one of which non-ionic polyol a1) include or For by polycondensation polymerisation by the carboxylic acid of 1,4:3,6-bis-dewatering hexitol and at least one diacid or higher functional and Other glycol optionally at least a kind of or polyol reaction and the polyalcohol that formed.
3. aqueous pu dispersions according to claim 1, at least one of which non-ionic polyol a1) include or For the carboxylic acid by making 1,4:3,6-bis-dewatering hexitol and at least one diacid or higher functional in polycondensation polymerisation, with And at least one other glycol or polyol reaction and the polyalcohol that formed.
4. the aqueous pu dispersions according to Claims 2 or 3, wherein said glycol is selected from: 1,2-ethylene glycol, 1,2- Propane diols, 1,3-propane diols, 1,4-butanediol, 1,5-pentanediol, 1,6-HD, 1,10-decanediol, 1,12-dodecane two Alcohol, 1,3 butylene glycol, 2,2-dimethyl-1,3-propane diols, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, dipropyl Glycol, tripropylene glycol, 1,4-and 1,6-hydroxymethyl-cyclohexane, C36-dimer diols, hydroxyl pivaloyl group hydroxyl front three Yl acetate and its ethoxylation and/or propenoxylated derivative, and wherein said polyalcohol is selected from: glycerine, three hydroxyl first Base propane, trimethylolethane, pentaerythrite, two glycerine, two-trimethylolpropane, two-pentaerythrite, D-sorbite and Ethoxylation and/or propenoxylated derivative.
5. the aqueous pu dispersions according to according to any one of claim 2-4, wherein said at least one diacid or more The carboxylic acid of Gao Guanneng is selected from: malonic acid, butanedioic acid, maleic acid, fumaric acid, itaconic acid, glutaric acid, citric acid, adipic acid, heptan two Acid, decanedioic acid, dodecanedioic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), naphthalene dicarboxylic acids, C36-dimer fatty Acid, C54-tripolymer aliphatic acid, trimellitic acid, PMA and anhydride ester derivs thereof.
6. aqueous pu dispersions according to claim 1, at least one of which non-ionic polyol a1) include or For being reacted or by making 1,4:3,6-bis-anhydrohexose with the monocarboxylic acid of hydroxyl-functional by making 1,4:3,6-bis-dewatering hexitol The polyalcohol that alcohol reacts with lactone, preferably caprolactone and formed.
7. aqueous pu dispersions according to claim 1, wherein said non-ionic polyol a1) by handing over third The ring-opening polymerisation of ester use 1,4:3,6-bis-dewatering hexitol formed as the initiator molecule of hydroxyl-functional.
8. the aqueous pu dispersions according to according to any one of claim 1-7, wherein said monohydric alcohol or polyalcohol a3) For the unsaturated monohydric alcohol of olefinic or the polyalcohol of isocyanate-reactive, it is selected from: polyester (methyl) acrylate, epoxy (first Base) acrylate, polyethers (methacrylate), polyurethane (methyl) acrylate and other comprise (methyl) propylene of hydroxyl Acid esters.
9. the aqueous pu dispersions according to according to any one of claim 1-8, wherein said Isosorbide-5-Nitrae: 3,6-bis-are dehydrated oneself Sugar alcohol is selected from: isobide, different mannide and different iditol.
10. aqueous pu dispersions according to claim 9, wherein Isosorbide-5-Nitrae: 3,6-bis-dewatering hexitols are different sorb Alcohol.
11. according to according to any one of claim 1-10 aqueous pu dispersions, it farther includes to serve as curable Diluent and the curable ethylenically unsaturated monomer in being present in the reaction of step i) as defined in claim 1.
12. aqueous pu dispersions according to according to any one of claim 1-11, wherein which is radiation-curable or The aqueous pu dispersions of peroxide-curable.
The 13. curable aqueous pu dispersions according to according to any one of claim 1-12, at least one of which is many Unit alkoxide component a), especially polyalcohol a1) have14The weight content of C so that14C/12C ratio is more than 0.1 × 10-12。
14. methods producing defined curable polyurethane aqueous dispersions as any one of claim 1-13, wherein The method comprises the following steps:
I) make to include that following at least one polyol component a) reacts with b) at least one polyisocyanates: a1) nonionic Polyalcohol, a2) there is at least one the ionic or potential ionic group including acid groups or its salt at least one polynary Alcohol and a3) the unsaturated monohydric alcohol of at least one olefinic and/or polyalcohol, the isocyanates of at least one of which polyisocyanates (NCO) hydroxyl (OH) group numbers relative to described at least one polyol component a) for the group numbers is excessive, Qi Zhongsuo State at least one polyol component a) to include, especially at non-ionic polyol a1) in, former from the carbon of renewable resource Son, preferably described polyalcohol a1) derived from Isosorbide-5-Nitrae: 3,6-bis-dewatering hexitols
Ii) at least in part, preferably entirely neutralize described polyalcohol a2 with nertralizer) acid groups, and stir with obtain Polyurethane prepolymer water-borne dispersions；With
Iii) by reacting with isocyanate-reactive chain extenders, make step ii) described prepolymer chain extension.
15. by as defined in claim 14, include step i) and ii) method obtainable polyurethane prepolymer water Property dispersion, it is in step ii) at the end of in step iii of chain extension) before obtain.
16. curable waterborne compositions, wherein said composition includes as defined according to any one of claim 1-13 Or by least one aqueous pu dispersions of the acquisition of method as defined according to claim 14 as curable Adhesive.
17. curable compositions according to claim 16, wherein said composition is selected from curable coating, especially Paint, varnish, ink composite, or selected from adhesive, sealant or cosmetic composition.
18. is defined or obtained by method as defined in claim 14 according to any one of claim 1-13 The purposes of water-based polyurethane polymer dispersion, wherein this water-based polyurethane polymer dispersion is used for coating, paint especially, Varnish, ink, or for adhesive, sealant or cosmetics.
The polyurethane of 19. solidifications, wherein the polyurethane of this solidification obtains freely defined or logical any one of claim 1-13 Cross the solidification of the aqueous pu dispersions that method as defined in claim 13 obtains.
The polyurethane of 20. solidifications according to claim 19, wherein the polyurethane of this solidification is used as coating, preferably acts as Paint, varnish and ink or be used as adhesive, be used as sealant or be used as cosmetics.
CN201580011153.9A 2014-02-28 2015-02-25 Curable aqueous polyurethane dispersions made from renewable resources Active CN106068293B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US201461946016P 2014-02-28 2014-02-28
US61/946,016 2014-02-28
US201461986170P 2014-04-30 2014-04-30
US61/986,170 2014-04-30
PCT/EP2015/053924 WO2015128373A1 (en) 2014-02-28 2015-02-25 Curable aqueous polyurethane dispersions made from renewable resources

Publications (2)

Publication Number Publication Date
CN106068293A true CN106068293A (en) 2016-11-02
CN106068293B CN106068293B (en) 2021-08-10

Family

ID=52574172

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201580011153.9A Active CN106068293B (en) 2014-02-28 2015-02-25 Curable aqueous polyurethane dispersions made from renewable resources

Country Status (7)

Country Link
US (1) US20160362515A1 (en)
EP (1) EP3110868B1 (en)
CN (1) CN106068293B (en)
ES (1) ES2773655T3 (en)
PL (1) PL3110868T3 (en)
TW (1) TWI565730B (en)
WO (1) WO2015128373A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112480350A (en) * 2020-11-06 2021-03-12 中国科学院化学研究所 Hydrophilic polyurethane, preparation method thereof, biological printing composite material and application
CN113015560A (en) * 2018-10-10 2021-06-22 科思创知识产权两合公司 Polyurethaneurea dispersions derived at least in part from renewable resources and their production and use
CN113950498A (en) * 2019-06-18 2022-01-18 湛新比利时股份有限公司 Biobased polyurethane (meth) acrylates for coatings
CN116888230A (en) * 2021-02-17 2023-10-13 株式会社三养社 Coating composition for metal with improved oil resistance and adhesion, method for preparing the same, and metal article coated therewith

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL3137530T3 (en) * 2014-04-30 2020-09-07 Arkema France Curable aqueous polyurethane dispersions made from renewable resources.
CN105885004A (en) * 2016-06-22 2016-08-24 江南大学 Bio-based photo-curable polyurethane and photoresist prepared with same
WO2018058016A1 (en) * 2016-09-25 2018-03-29 Myriant Corporation Biorenewable high performance polyester polyols
US10573772B2 (en) * 2017-05-22 2020-02-25 Swift Engineering, Inc. Composite vehicle skin co-cured with solar-cell array
EP3700975B1 (en) * 2017-10-25 2023-12-06 Sun Chemical Corporation Actinically curable adhesive composition with improved properties
CN107857869B (en) * 2017-11-27 2018-08-28 上海金狮化工有限公司 Aqueous polyurethane and its preparation method and application
WO2020122954A1 (en) * 2018-12-14 2020-06-18 Hewlett-Packard Development Company, L.P. Textile printing
JP7459626B2 (en) 2020-04-02 2024-04-02 ａｒｔｉｅｎｃｅ株式会社 Water-based gravure or flexographic inks and their uses
TW202200655A (en) * 2020-06-23 2022-01-01 日商Ｄｉｃ股份有限公司 Urethane resin composition, leather film, and synthetic leather wherein the urethane resin composition contains an anionic urethane resin and water
CN114517035B (en) * 2021-12-29 2023-04-14 广东大自然家居科技研究有限公司 Water-based plant-based varnish, preparation method thereof and woodware
US11530332B1 (en) * 2022-07-12 2022-12-20 Evoco Limited Biobased aqueous polyurethane dispersions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6162506A (en) * 1997-05-31 2000-12-19 Basf Coatings Ag Aqueous coating materials and methods of making and using same
CN101048477A (en) * 2004-10-26 2007-10-03 诺誉有限公司 Water-borne dispersions of oil modified urethane polymers
CN101198631A (en) * 2005-06-17 2008-06-11 赖克霍德公司 Radiation curable polyurethane dispersions
CN102812062A (en) * 2010-03-02 2012-12-05 拜耳知识产权有限责任公司 Aqueous polyurethane dispersions
EP2644634A1 (en) * 2012-03-30 2013-10-02 Cytec Surface Specialties, S.A. Radiation curable (meth)acrylated compounds

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6140422A (en) * 1998-04-23 2000-10-31 E.I. Dupont De Nemours And Company Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers
GB0207345D0 (en) * 2002-03-28 2002-05-08 Unichema Chemie Bv Polyurethane
EP1845143A1 (en) * 2006-04-14 2007-10-17 Cytec Surface Specialties, S.A. Aqueous radiation curable polyurethane compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6162506A (en) * 1997-05-31 2000-12-19 Basf Coatings Ag Aqueous coating materials and methods of making and using same
CN101048477A (en) * 2004-10-26 2007-10-03 诺誉有限公司 Water-borne dispersions of oil modified urethane polymers
CN101198631A (en) * 2005-06-17 2008-06-11 赖克霍德公司 Radiation curable polyurethane dispersions
CN102812062A (en) * 2010-03-02 2012-12-05 拜耳知识产权有限责任公司 Aqueous polyurethane dispersions
EP2644634A1 (en) * 2012-03-30 2013-10-02 Cytec Surface Specialties, S.A. Radiation curable (meth)acrylated compounds

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113015560A (en) * 2018-10-10 2021-06-22 科思创知识产权两合公司 Polyurethaneurea dispersions derived at least in part from renewable resources and their production and use
CN113950498A (en) * 2019-06-18 2022-01-18 湛新比利时股份有限公司 Biobased polyurethane (meth) acrylates for coatings
CN112480350A (en) * 2020-11-06 2021-03-12 中国科学院化学研究所 Hydrophilic polyurethane, preparation method thereof, biological printing composite material and application
CN112480350B (en) * 2020-11-06 2022-04-05 中国科学院化学研究所 Hydrophilic polyurethane, preparation method thereof, biological printing composite material and application
CN116888230A (en) * 2021-02-17 2023-10-13 株式会社三养社 Coating composition for metal with improved oil resistance and adhesion, method for preparing the same, and metal article coated therewith

Also Published As

Publication number Publication date
TW201546117A (en) 2015-12-16
WO2015128373A1 (en) 2015-09-03
TWI565730B (en) 2017-01-11
CN106068293B (en) 2021-08-10
ES2773655T3 (en) 2020-07-14
US20160362515A1 (en) 2016-12-15
EP3110868A1 (en) 2017-01-04
PL3110868T3 (en) 2020-05-18
EP3110868B1 (en) 2019-11-13

Similar Documents

Publication Publication Date Title
CN106068293A (en) The curable aqueous pu dispersions being manufactured by renewable resource
EP3137530B1 (en) Curable aqueous polyurethane dispersions made from renewable resources.
US11629217B2 (en) Vegetable oil-modified, hydrophobic polyurethane dispersions
EP3137563B1 (en) Nail polish composition based on solvent-free aqueous polyurethane dispersions
US11299614B2 (en) Sustainable, energy-curable polyester polyols and coatings or rigid foams therefrom
WO2009134388A1 (en) Uv/eb curable biobased coating for flooring application
US20160304742A1 (en) Solvent-free aqueous polyurethane dispersions and methods of producing solvent-free aqueous polyurethane dispersions
EP3580249B1 (en) Aqueous coating composition
KR101710217B1 (en) Polyurethane dispersion, method of producing the same, coated articles, and method for coating articles
CA3196781A1 (en) Aqueous bio-based energy curable polyurethane composition
EP2768901A1 (en) Polyester polyol resins compositions
JP7110029B2 (en) Hydrophilic polyisocyanate composition, curing agent composition and aqueous coating composition
EP2900721B1 (en) Urethane alkyd comprising strong acidic groups

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant